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Chapter 1. Introduction commercial lithium-ion batteries were released in 1990, which initiated the widespread use of secondary batteries in everything from small user electronics to cars and stationary energy storage [10, 11]. There are, however, several challenges with Li-ion batteries. The high energy density and use of flammable organic electrolytes in the batteries make them inherently dangerous if designed poorly or misused, which has led to numerous incidents where the Li-ion batteries of consumer electronics and cars have caught fire [12, 13]. Furthermore, because the power and energy of these encapsulated secondary batteries are coupled through the active material in the electrodes, a doubling of the stored energy in theory leads to a doubling of the power, and therefore a doubling of the price. This means that the capital expenditure (CAPEX) per energy unit does not benefit directly from increasing the total discharge time. Another electrochemical storage technology that has been explored over the past ∼50 years is the redox flow battery (RFB). In contrast to encapsulated secondary batteries, the energy is stored in redox-active materials dissolved in two separate electrolytes that are pumped from reservoirs through an electrochemical reactor, making them a hybrid between a reversible fuel cell and an encapsulated secondary battery. This makes it possible to scale power and energy independently, which leads to a decrease in CAPEX per energy unit with increasing discharge time [14], as illustrated in Figure 1.1. For large enough volumes of electrolyte (i.e. high discharge times), the CAPEX per energy unit approaches that of the electrolytes. Electrolyte cost Discharge time [h] −→ Initial costs stack, pumps, tanks, etcà Encapsulated secondary batteries Figure 1.1: Qualitative illustration of the CAPEX against discharge time of encapsulated secondary batteries (e.g. Li-ion) and flow batteries. Adapted from [14]. Many types of chemistries have been investigated for use in RFBs, with the vanadium redox flow battery (VRFB) being the most studied and most widely commercialised. The electrolytes consist of vanadium salts dissolved in sulfuric acid and utilise the shuttling between V2+/V3+ on the negative side and V4+/V5+ on the positive side of the battery to store energy. Over 180 major VRFB projects have been commissioned around the world, with powers and energies ranging from 600 W–15 MW and 1.8 kW h–60 MW h [15]. A 200MW/800MWh system is currently under construction in Dalian, China, which will be the world’s largest battery once finished [16]. The main reason why VRFBs have not achieved a higher degree of market penetration is the price; the current CAPEX is in the area of $300–500(kWh)−1 [17–19], as compared to ∼$310(kWh)−1 for state- 2 CAPEX [$ (kW h)−1] −→ Flow batteriesPDF Image | Organic Redox Flow Batteries 2023
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